CN113461869A - Metal organic framework-calcium carbonate composite crystal material and preparation method thereof - Google Patents
Metal organic framework-calcium carbonate composite crystal material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a metal organic framework-calcium carbonate composite crystal material and a preparation method thereof, belonging to the technical field of nano composite materials. The metal organic framework-calcium carbonate composite crystal material can be obtained by performing macromolecular modification on the surface of metal organic framework crystal particles, then adding the metal organic framework crystal particles into a calcium chloride aqueous solution, and synthesizing calcium carbonate crystals by an ammonia diffusion method. In the composite crystal material, the metal organic framework particles can be uniformly embedded in the inorganic calcium carbonate crystals, so that the thermal stability and the alkali stability of the composite crystal material are greatly improved, and the composite crystal material has important application values in the technical fields of catalysis, printing ink, coating, proton conduction and biomedicine.
Description
Technical Field
The invention relates to a metal organic framework-calcium carbonate composite crystal material and a preparation method thereof, belonging to the technical field of nano composite materials.
Background
Calcium carbonate is a mineral with abundant content, is used as a high-quality filler and white pigment, has the characteristics of low cost, excellent performance, no toxicity, no odor and the like, and is widely applied to the fields of rubber, plastics, papermaking, printing ink, coating, sealant, adhesive, medicine, toothpaste, food and the like. However, calcium carbonate has the defects that the calcium carbonate has the characteristics of high surface energy, high possibility of agglomeration, surface hydrophilicity, oleophobicity and strong polarity, has weak bonding force with a base material, and is easy to cause surface and interface collapse.
Metal Organic Frameworks (MOFs) are crystalline porous materials composed of organic ligands and metal ions (or clusters), and have the advantages of diverse structures, strong designability, high specific surface area and the like. However, in practical applications, the metal organic framework material is subject to the defects of easy collapse of crystal structure, large influence of environmental humidity on performance, and the like, and the adsorption performance needs to be improved. Researches find that the metal organic framework can be used as a material matrix to be combined with a plurality of inorganic particles with different properties to form the core-shell type composite nano material, and the application range of the two materials is further expanded. There are generally two ways of combining inorganic particles with metal organic frameworks: 1) firstly, synthesizing a metal organic framework, and then generating inorganic particles in situ in a pore channel of the metal organic framework; 2) firstly synthesizing inorganic particles, and synthesizing the inorganic particles and the metal organic framework core-shell composite material by using the inorganic particles as nucleation centers. The existing synthesis method is difficult to realize the complete and uniform wrapping of the metal organic framework on the large-size inorganic particles, and the encapsulation rate of the core-shell composite material is low.
Because the metal organic framework and the calcium carbonate have interfacial incompatibility, the traditional method is difficult to effectively compound the two different substances, the invention prepares a novel metal organic framework-calcium carbonate composite material, realizes the integration of different components and functions, and has important application value.
Disclosure of Invention
The invention provides a metal organic framework-calcium carbonate composite crystal material and a preparation method thereof, wherein in the composite crystal material, the metal organic framework can be uniformly embedded in an inorganic calcium carbonate crystal, so that the problem of interface incompatibility between the metal organic framework and calcium carbonate at present is solved, and a novel method for embedding the metal organic framework in the inorganic calcium carbonate crystal is provided.
In order to achieve the purpose, the invention provides the following scheme:
the technical scheme is as follows:
a metal organic framework-calcium carbonate composite crystal material is characterized in that metal organic framework crystal particles are embedded in calcium carbonate crystals.
The second technical proposal is that:
a preparation method of a metal organic framework-calcium carbonate composite crystal material comprises the following steps:
modifying the metal organic framework crystal particles by a chain transfer agent, further polymerizing the monomers to obtain polymer modified metal organic framework crystal particles, adding the polymer modified metal organic framework crystal particles into a calcium chloride aqueous solution, and reacting by an ammonia diffusion method to obtain the metal organic framework-calcium carbonate composite crystal material.
Further, the metal organic framework crystal particles (UiO-66-NH)2) The preparation method is carried out by adopting a hot solvent method and comprises the following specific steps:
zirconium tetrachloride (ZrCl)4) And 2-aminoterephthalic acid (NH)2-BDC) are respectively dissolved by solvent and then mixed evenly, acid solution is added, and the mixture is centrifugally washed by solvent and water in sequence after the reaction is finished to obtain the metal organic framework (UiO-66-NH)2) Crystal particles.
Further, the metal organic framework (UiO-66-NH)2) The grain diameter of the crystal particles is 100-800nm and the chemical formula is Zr6O4(OH)4(BDC-NH2)6。
Further, the zirconium tetrachloride (ZrCl)4) With 2-amino-p-benzeneDicarboxylic acid (NH)2-BDC) in a mass ratio of 3-5:5-7, zirconium tetrachloride (ZrCl)4) The feed-liquid ratio of the solvent is 3-5g: 40000mL of zirconium tetrachloride (ZrCl)4) The material-liquid ratio of the acid solution is 3-5g:400-600 mL.
Further, the acid solution comprises one or more of acetic acid, formic acid, or triethylamine.
Further, the solvent comprises one or more of N, N-Dimethylformamide (DMF) or an alcohol solvent.
Further, the reaction condition is 30-120 ℃, and the reaction lasts for 2-4 h.
Further, the macromolecule modified metal organic framework crystal particles are obtained by modifying with a chain transfer agent, and the specific steps are as follows:
metal organic framework (UiO-66-NH)2) Adding a chain transfer agent into the crystal particles, stirring the crystal particles and a catalyst to perform a first reaction, washing the crystal particles by using an alcohol solution, adding an initiator and a polymerizable monomer, introducing an inert gas to remove oxygen, stirring the mixture to perform a second reaction, and dispersing the mixture by using water to obtain the polymer modified metal organic framework crystal particles.
Further, the terminal group of the chain transfer agent contains a carboxyl group.
Further, the catalyst is 1-hydroxybenzotriazole (HOBt) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) in a mass ratio of 2-3: 3-4.
Further, the initiator is an azo initiator.
Further, the initiator comprises that the initiator comprises azobiscyanovaleric acid and/or azobisisobutyronitrile. Azo initiators such as azobiscyanovaleric acid and azobisisobutyronitrile.
Further, the polymerizable monomer includes one or more of methacrylic acid (MAA), acrylic acid, 2- (phosphonooxy) ethyl methacrylate, or 2- (sulfooxy) ethyl methacrylate ammonium salt.
Further, the mass ratio of the metal organic framework crystal particles, the chain transfer agent and the catalyst is 2-6:4-5:5-7, and the mass ratio of the initiator, the polymerizable monomer and the chain transfer agent is 1:150-155: 12-14.
Further, the first reaction temperature is 100-120 ℃, the reaction time is 24h, the stirring speed is 2500-3500rpm, the second reaction temperature is 60-80 ℃, the reaction time is 24h, and the stirring speed is 2000-3000 rpm.
Further, the concentration of the calcium chloride aqueous solution is 1-20mM, and the mass fraction of the polymer modified metal organic framework crystal particles is 0.01% -1%.
Further, the calcium chloride aqueous solution and the polymer-modified metal-organic framework crystal particles react in a closed environment, ammonia gas and carbon dioxide are generated through decomposition of ammonium carbonate in the closed environment to trigger crystallization of calcium carbonate, and the metal-organic framework crystal particles are adsorbed and embedded into the calcium carbonate crystals in the formation process of the calcium carbonate crystals.
The third technical scheme is as follows:
the metal organic framework-calcium carbonate composite crystal material is applied to the fields of catalysis, printing ink, coating, proton conduction and biomedicine.
The invention discloses the following technical effects:
1) the invention uses a chain transfer agent with a terminal group containing carboxylic acid and a metal organic framework (UiO-66-NH)2) The amino group on the surface of the crystal particles reacts, then high molecular chains are grafted through reversible addition-fragmentation transfer polymerization, and the polymer modified metal organic framework crystal particles are efficiently and uniformly embedded into the calcium carbonate crystals through an ammonia diffusion method to obtain a composite crystal material with a special structure, so that the composition of the metal organic framework and the calcium carbonate crystals is realized.
2) The invention greatly improves the thermal stability and the alkali stability of the metal organic framework crystal by carrying out macromolecular modification on the surface of the metal organic framework crystal and then embedding the metal organic framework crystal into the inorganic calcium carbonate crystal. By embedding guest metal organic framework particles in the calcium carbonate host crystal, integration of different components and functions is realized, and the calcium carbonate host crystal has important application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 shows the metal organic framework (UiO-66-NH) prepared in example 12) Transmission electron micrographs of the crystal particles;
FIG. 2 shows the metal-organic framework (UiO-66-NH) prepared in example 12) Size (diameter) profile of crystal particles;
FIG. 3 is an optical microscope photograph of a metal organic framework-calcium carbonate composite crystalline material prepared in example 1;
FIG. 4 is a scanning electron microscope image of the metal organic framework-calcium carbonate composite crystal material prepared in example 1;
FIG. 5 is an internal scanning electron microscope image of the metal organic framework-calcium carbonate composite crystalline material prepared in example 1;
FIG. 6 is an internal scanning electron microscope image of the metal organic framework-calcium carbonate composite crystalline material prepared in comparative example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The technical solution of the present invention is further illustrated by the following examples.
In the embodiment of the invention, the calcium carbonate crystal growth is carried out by an ammonia diffusion method, which specifically comprises the following steps: ammonium carbonate decomposes to produce ammonia gas and carbon dioxide gas, which enter an aqueous solution of calcium chloride to trigger the growth of calcium carbonate crystals.
Example 1
0.204g of ZrCl4Dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, 0.29g of NH2-BDC (2-aminoterephthalic acid) is dissolved in 100mL DMF (N, N-dimethylformamide) solvent, then the two are mixed and 24mL glacial acetic acid is added, the mixture is reacted for 3h in 120 ℃ oil bath, and then DMF is used for centrifugation to obtain the metal organic framework (UiO-66-NH)2) Crystal particles of the metal-organic framework (UiO-66-NH)2) Transmission electron microscopy of the Crystal particles As shown in FIG. 1, measurement of the Metal organic framework (UiO-66-NH) by dynamic light Scattering2) The size (diameter) distribution of the crystal particles is shown in FIG. 2, and the metal organic framework (UiO-66-NH) is shown2) Straightening of crystal particlesThe diameter is between 100 and 800 nm;
then, 0.5g of UiO-66-NH was taken2Dispersing the mixture into 80mL of DMF solvent, adding 0.448g of chain transfer agent CPCP (4-cyano-4- (phenylthiocarbonylthio) pentanoic acid), 0.238g of HOBt (1-hydroxybenzotriazole) and 0.368g of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) in sequence, reacting in an oil bath at 120 ℃ for 24h, and centrifuging at 2500rpm by using methanol after the reaction is finished to obtain UiO-66-NH with the surface modified by the chain transfer agent2Crystal particles; subsequently, chain transfer agent modified UiO-66-NH is added2Dispersing the crystal particles into 80mL of methanol, adding 5.516g of monomer MAA (methacrylic acid) and 35.92mg of azodicyano valeric acid in sequence, introducing nitrogen to remove oxygen, carrying out oil bath reaction at 70 ℃ for 24h, centrifuging at 2500rpm with water, and dispersing into water to obtain polymer modified UiO-66-NH2Crystal particles;
finally, 10mL of 3mM calcium chloride aqueous solution is prepared, and 0.1% by mass of macromolecule modified UiO-66-NH is added25mL of crystal particles react in a closed container, ammonium carbonate is used for decomposing to generate ammonia gas and carbon dioxide to trigger the formation of calcium carbonate, and the polymer modified UiO-66-NH2The crystal particles are spontaneously embedded into the calcium carbonate to obtain the metal organic framework-calcium carbonate composite crystal material, and the crystal form of the obtained calcium carbonate is calcite.
The optical microscopic image of the metal organic framework-calcium carbonate composite crystal material prepared in example 1 is shown in fig. 3, the low-power scanning electron microscopic image is shown in fig. 4, the high-power scanning electron microscopic image is shown in fig. 5, and it can be seen from fig. 4 and 5 that the polymer-modified metal organic framework crystal particles are uniformly dispersed and embedded in the calcium carbonate crystals.
Example 2
0.15g of ZrCl4Dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, 0.35g of NH2-BDC (2-aminoterephthalic acid) is dissolved in 100mL DMF (N, N-dimethylformamide) solvent, then the two are mixed and 20mL formic acid is added, and the mixture is reacted in an oil bath at 80 ℃ for 2h, and then centrifuged with DMF (N, N-dimethylformamide) to obtain a metal organic framework (UiO-66-NH)2) Crystal particles;
then, 0.0625g of UiO-66-NH was sampled2Dispersing the mixture into 10mL of DMF solvent, adding 0.056g of chain transfer agent CPCP (4-cyano-4- (phenylthiocarbonylthio) pentanoic acid), 0.02976g of HOBt (1-hydroxybenzotriazole) and 0.046g of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) in sequence, reacting in an oil bath at 100 ℃ for 24h, and centrifuging at 3000rpm by using methanol after the reaction is finished to obtain UiO-66-NH with the surface modified by the chain transfer agent2Crystal particles; subsequently, chain transfer agent modified UiO-66-NH is added2Dispersing the crystal particles into 10mL of methanol, sequentially adding 0.6895g of monomer acrylic acid and 4.49mg of azobisisobutyronitrile, introducing nitrogen to remove oxygen, carrying out oil bath reaction at 80 ℃ for 24h, centrifuging at 3000rpm with water, and dispersing in water to obtain polymer-modified UiO-66-NH2Crystal particles;
finally, 10mL of 15mM calcium chloride aqueous solution is prepared, and 0.5% by mass of macromolecule modified UiO-66-NH is added25mL of crystal particles react in a closed container, ammonia gas and carbon dioxide generated by decomposing ammonium carbonate are used for triggering the formation of calcium carbonate, so that the metal organic framework-calcium carbonate composite crystal material is obtained, and the crystal form of the obtained calcium carbonate is calcite.
Example 3
0.25g of ZrCl4Dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, 0.25g of NH2-BDC (2-amino terephthalic acid) is dissolved in 100mL of methanol solvent, then the two are mixed and 30mL of triethylamine is added, the mixture is reacted for 4h in an oil bath at 30 ℃, and then the mixture is centrifuged by using the methanol solvent to obtain the metal organic framework (UiO-66-NH)2) Crystal particles;
then, 0.0625g of UiO-66-NH was sampled2Dispersing the mixture into 10mL of methanol solvent, adding 0.112g of chain transfer agent CPCP (4-cyano-4- (phenylthiocarbonylthio) pentanoic acid), 60mg of 0.06g of HOBt (1-hydroxybenzotriazole) and 92mg of 0.092g of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) in sequence, reacting in an oil bath at 120 ℃ for 24h, and centrifuging at 3500rpm by using methanol after the reaction to obtain UiO-66-NH modified by the chain transfer agent on the surface2Crystal particles; subsequently, chain transfer agent modified UiO-66-NH is added2Crystal particleDispersing the particles into 10mL of methanol, sequentially adding 1.379g of monomer 2- (phosphonooxy) ethyl methacrylate and 8.98mg of azodicyano valeric acid, introducing nitrogen to remove oxygen, carrying out oil bath reaction at 60 ℃ for 24h, centrifuging at 2000rpm with water, and dispersing in water to obtain the polymer modified UiO-66-NH2Crystal particles;
finally, preparing 10mL of 20mM calcium chloride aqueous solution, and adding 1% by mass of macromolecule modified UiO-66-NH25mL of crystal particles react in a closed container, ammonia gas and carbon dioxide generated by decomposing ammonium carbonate are used for triggering the formation of calcium carbonate, so that the metal organic framework-calcium carbonate composite crystal material is obtained, and the crystal form of the obtained calcium carbonate is calcite.
Example 4
0.15g of ZrCl4Dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, 0.35g of NH2-BD (2-aminoterephthalic acid) C was dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, and then the two were mixed and added with 30mL of glacial acetic acid, reacted in an oil bath at 120 ℃ for 3 hours, followed by centrifugation with DMF (N, N-dimethylformamide) to obtain a metal organic framework (UiO-66-NH)2) Crystal particles;
then, 0.5g of UiO-66-NH was taken2Dispersing the mixture into 80mL of DMF solvent, adding 1.25g of chain transfer agent CPCP (4-cyano-4- (phenylthiocarbonylthio) pentanoic acid), 0.875g of HOBt (1-hydroxybenzotriazole) and 0.875g of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) in sequence, reacting in an oil bath at 120 ℃ for 24h, and centrifuging at 2500rpm by using methanol after the reaction is finished to obtain UiO-66-NH with the surface modified by the chain transfer agent2Crystal particles; subsequently, chain transfer agent modified UiO-66-NH is added2Dispersing the crystal particles into 80mL of methanol, sequentially adding 13.4g of monomer 2- (sulfo-oxo) ethyl methacrylate ammonium salt and 104.1mg of azodiisobutyronitrile, introducing nitrogen to remove oxygen, carrying out oil bath reaction at 70 ℃ for 24h, centrifuging at 2500rpm with water, and dispersing into water to obtain polymer-modified UiO-66-NH2Crystal particles;
finally, 10mL of 3mM calcium chloride aqueous solution is prepared, and 0.01 percent of macromolecule modified UiO-66-NH is added25mL of crystal particles react in a closed container, ammonium carbonate is used for decomposing to generate ammonia gas and carbon dioxide to trigger the formation of calcium carbonate, and the polymer modified UiO-66-NH2The crystal particles are spontaneously embedded into the calcium carbonate to obtain the metal organic framework-calcium carbonate composite crystal material, and the crystal form of the obtained calcium carbonate is calcite.
Example 5
0.25g of ZrCl4Dissolved in 100mL of DMF (N, N-dimethylformamide) solvent, 0.25g of NH2-BDC (2-aminoterephthalic acid) was dissolved in 100mL DMF (N, N-dimethylformamide) solvent, then the two were mixed and added with 12mL glacial acetic acid, reacted in an oil bath at 50 ℃ for 3.5h, and then centrifuged with DMF (N, N-dimethylformamide) to obtain metal organic framework (UiO-66-NH)2) Crystal particles;
then, 0.5g of UiO-66-NH was taken2Dispersing the mixture into 80mL of DMF solvent, adding 0.34g of chain transfer agent CPCP (4-cyano-4- (phenylthiocarbonylthio) pentanoic acid), 0.14g of HOBt (1-hydroxybenzotriazole) and 0.28g of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) in sequence, reacting in an oil bath at 120 ℃ for 24h, and centrifuging at 2500rpm by using methanol after the reaction is finished to obtain UiO-66-NH with the surface modified by the chain transfer agent2Crystal particles; subsequently, chain transfer agent modified UiO-66-NH is added2Dispersing the crystal particles into 80mL of methanol, adding 4.4g of MAA (methacrylic acid) monomer and 23.78mg of azobiscyanovaleric acid in sequence, introducing nitrogen to remove oxygen, carrying out oil bath reaction at 70 ℃ for 24h, centrifuging at 2500rpm with water, and dispersing into water to obtain polymer modified UiO-66-NH2Crystal particles;
finally, 10mL of 3mM calcium chloride aqueous solution is prepared, and 0.6% of macromolecule modified UiO-66-NH is added25mL of crystal particles react in a closed container, ammonium carbonate is used for decomposing to generate ammonia gas and carbon dioxide to trigger the formation of calcium carbonate, and the polymer modified UiO-66-NH2The crystal particles are spontaneously embedded into the calcium carbonate to obtain the metal organic framework-calcium carbonate composite crystal material, and the crystal form of the obtained calcium carbonate is calcite.
Comparative example 1
The only difference from example 1 is that isopropanol is used to replace chain transfer agent, the inside of the product is subjected to electron microscope scanning, the electron microscope scanning is shown in FIG. 6, and as can be seen from FIG. 6, only calcium carbonate crystal, macromolecule modified metal organic framework (UiO-66-NH) can be obtained under the condition2) The crystal particles cannot be embedded within the calcium carbonate crystals.
Comparative example 2
The same as example 1, except that EDC alone was used as the catalyst, and the experimental results were the same as comparative example 1, i.e., the polymer-modified metal organic framework (UiO-66-NH)2) The crystal particles cannot embed calcium carbonate crystals.
Comparative example 3
The experimental results were the same as in comparative example 1, i.e., the polymer-modified metal organic framework (UiO-66-NH), except that cyclohexane was used as the solvent in example 12) The crystal particles cannot embed calcium carbonate crystals.
As can be seen from comparative examples 1 to 3, the change in experimental conditions resulted in the failure to form the metal organic framework-calcium carbonate composite crystalline material of the present invention.
Performance testing
a. The thermo-gravimetric analysis instrument TGA-1150 was used to perform the thermo-gravimetric temperature and thermal stability tests on the metal organic framework-calcium carbonate composite crystal materials prepared in examples 1-5, and a blank control group was set as unmodified metal organic framework crystal particles, and the results are shown in Table 1.
TABLE 1 thermo-gravimetric temperatures of various groups of metal-organic frameworks
| Group of | Temperature of thermal weight loss (. degree.C.) |
| Example 1 | 680 |
| Example 2 | 678 |
| Example 3 | 678 |
| Example 4 | 679 |
| Example 5 | 679 |
| Blank control group | 355 |
As can be seen from the data in Table 1, by comparing UiO-66-NH2The surface of the crystal is modified by high polymer, and then the crystal is embedded into inorganic calcium carbonate crystal, thereby greatly improving the thermal stability.
b. Carrying out alkali resistance test on the metal organic framework-calcium carbonate composite crystal materials prepared in the embodiments 1-5, soaking the metal organic framework-calcium carbonate composite crystal materials prepared in each group in water with the pH value of 8 for 1 day to 15 days, and keeping the metal organic framework-calcium carbonate composite crystal materials prepared in the embodiments 1-5 in a perfect shape after 15 days; while pure metal organic framework nanoparticles (UiO-66-NH)2) The organic framework-calcium carbonate composite crystal material prepared by the method has good alkali stability.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The metal organic framework-calcium carbonate composite crystal material is characterized in that metal organic framework crystal particles are embedded in calcium carbonate crystals, and macromolecular chains are grafted on the surfaces of the metal organic framework crystal particles.
2. A method for preparing a metal organic framework-calcium carbonate composite crystalline material according to claim 1, comprising the steps of:
modifying the metal organic framework crystal particles by a chain transfer agent, further polymerizing the monomers to obtain polymer modified metal organic framework crystal particles, adding the polymer modified metal organic framework crystal particles into a calcium chloride aqueous solution, and reacting by an ammonia diffusion method to obtain the metal organic framework-calcium carbonate composite crystal material.
3. The method for preparing the metal organic framework-calcium carbonate composite crystal material according to claim 2, wherein the metal organic framework crystal particles are prepared by a hot solvent method, and the method comprises the following specific steps:
respectively dissolving zirconium tetrachloride and 2-amino terephthalic acid by using solvents, uniformly mixing, adding an acid solution, and after the reaction is finished, sequentially centrifugally washing by using the solvents and water to obtain the metal organic framework crystal particles.
4. The method for preparing a metal organic framework-calcium carbonate composite crystal material according to claim 3, wherein the mass ratio of the zirconium tetrachloride to the 2-amino terephthalic acid is 3-5:5-7, and the feed-liquid ratio of the zirconium tetrachloride to the solvent is 3-5g: 4000mL, wherein the material-liquid ratio of the zirconium tetrachloride to the acid solution is 3-5g:400-600 mL;
the acid solution comprises one or more of acetic acid, formic acid or triethylamine;
the solvent comprises one or more of N, N-dimethylformamide or an alcohol solvent;
the reaction temperature is 30-120 ℃ and the reaction time is 2-4 h.
5. The preparation method of the metal organic framework-calcium carbonate composite crystal material as claimed in claim 2, wherein the polymer modified metal organic framework crystal particles are obtained by modifying with a chain transfer agent and further polymerizing monomers, and the preparation method comprises the following specific steps:
firstly, adding a chain transfer agent and a catalyst into a metal organic framework crystal particle dispersion liquid, stirring to perform a first reaction, and washing with an alcohol solution to obtain a metal organic framework modified by the chain transfer agent; and then adding an initiator and a polymerizable monomer, introducing inert gas, stirring for a second reaction, and dispersing with water to obtain the polymer modified metal organic framework crystal particles.
6. The method for preparing a metal organic framework-calcium carbonate composite crystalline material according to claim 5, wherein the terminal group of the chain transfer agent contains a carboxyl group.
The catalyst is 1-hydroxybenzotriazole and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and the mass ratio is 2-3: 3-4;
the initiator comprises azobiscyanovaleric acid and/or azobisisobutyronitrile;
the polymerizable monomer comprises one or more of methacrylic acid, acrylic acid, 2- (phosphonooxy) ethyl methacrylate or 2- (sulfooxy) ethyl methacrylate ammonium salt.
7. The method for preparing a metal organic framework-calcium carbonate composite crystal material as claimed in claim 5, wherein the mass ratio of the metal organic framework crystal particles, the chain transfer agent and the catalyst is 2-6:4-5:5-7, and the mass ratio of the initiator, the polymerizable monomer and the chain transfer agent is 1:150-155: 12-14;
the first reaction temperature is 100-120 ℃, the reaction time is 24h, the stirring speed is 2500-3500rpm, the second reaction temperature is 60-80 ℃, the reaction time is 24h, and the stirring speed is 2000-3000 rpm.
8. The method for preparing the metal organic framework-calcium carbonate composite crystal material according to claim 2, wherein the concentration of the calcium chloride aqueous solution is 1-20mM, and the mass fraction of the polymer modified metal organic framework crystal particles is 0.01% -1%.
9. The method for preparing the metal organic framework-calcium carbonate composite crystal material according to claim 2, wherein the calcium chloride aqueous solution and the polymer modified metal organic framework crystal particles are reacted in a closed environment.
10. The use of the metal organic framework-calcium carbonate composite crystalline material of claim 1 in catalysis, inks, coatings, proton conduction, and biomedical applications.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498695A (en) * | 2015-12-02 | 2016-04-20 | 南京师范大学 | Sodium alginate-MOF (metal organic framework) composite spherule as well as preparation method and application thereof |
| CN109336512A (en) * | 2018-11-29 | 2019-02-15 | 中南大学 | A kind of nano metal organic frame wall material and preparation method thereof |
| CN109589932A (en) * | 2018-12-13 | 2019-04-09 | 常州大学 | A kind of carbon nanotube/UiO-66-NH2The preparation method of nanocomposite |
| CN111151224A (en) * | 2020-01-07 | 2020-05-15 | 天津大学 | Metal organic framework with polymer grafted on surface and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498695A (en) * | 2015-12-02 | 2016-04-20 | 南京师范大学 | Sodium alginate-MOF (metal organic framework) composite spherule as well as preparation method and application thereof |
| CN109336512A (en) * | 2018-11-29 | 2019-02-15 | 中南大学 | A kind of nano metal organic frame wall material and preparation method thereof |
| CN109589932A (en) * | 2018-12-13 | 2019-04-09 | 常州大学 | A kind of carbon nanotube/UiO-66-NH2The preparation method of nanocomposite |
| CN111151224A (en) * | 2020-01-07 | 2020-05-15 | 天津大学 | Metal organic framework with polymer grafted on surface and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230427A (en) * | 2021-12-06 | 2022-03-25 | 天津大学 | Composite fuel, preparation method thereof and propellant containing same |
| CN114230427B (en) * | 2021-12-06 | 2022-10-04 | 天津大学 | Composite fuel, preparation method thereof and propellant containing same |
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